The present invention generally relates to fluid treating and, more particularly, to methods which are especially adapted for providing for improved treatment of fluids. Although capable of a variety of uses, this invention finds advantageous utility in the treatment of water to remove undesirable constituents contained therein such as, for example, dissolved chlorine and nitrates constituents.
In the field of fluid treating, and particularly in the field of treating water for commercial, industrial and domestic use, a number of systems have been proposed, some or all of which have certain undesirable characteristics, drawbacks or disadvantages associated therewith.
For example, ion-exchange systems are commonly used to soften water and selectively remove specific impurities from the water. The active medium of the ion-exchanger is an ion-exchange resin which is designed to remove undesirable constituents from the fluid and replace those undesirable constituents with a less undesirable constituent. For instance, a cation exchange resin employed to remove the hardness-producing elements of calcium and magnesium may be designed to simultaneously give up sodium in exchange for the calcium and magnesium contained in the water which has passed through the ion-exchanger. Regardless of the specific ion-exchange resin used, eventually the bed of resin becomes exhausted and the unit must be removed from service and be regenerated to become useful again. In addition to exhaustion the resin is also susceptible to chemical degradation. Accordingly, the ion-exchanger unit must be carefully maintained and monitored to assure continued acceptable performance.
Another popular type of process for treating water is reverse osmosis wherein pressure in excess of the osmotic pressure of the fluid is used to force untreated water, normally at ambient temperature, through a selective membrane in a direction opposite to that normally observed in osmotic processes. The selective membrane is designed to allow the water to permeate through while rejecting the dissolved undesirable constituents. The success of this process depends in large part upon the development of suitable membranes. Membranes utilized in reverse osmosis typically experience a variety of temperature, chemical and pressure stability problems as well as speed and capacity limitations. For example, water supplies are commonly treated with chlorine as an antibacterial agent. The dissolved chlorine, although highly effective in combating bacteria, often has a deleterious effect on reverse osmosis membranes. Additionally, reverse osmotic equipment also must be carefully set up, maintained, and monitored. Accordingly, regardless of the sophistication of the technology used, if the end user fails to maintain the system and perform the necessary sampling required to ensure that the system is functioning to design specifications a breakdown in treatment can occur.
Still another popular water treatment process is the application of activated carbon, which is widely used for taste and odor control as well as removal of organic contaminants from water by adsorbtion since activated carbon is characterized by a high adsorbtivity for gases, vapors, and colloidal solids. However, similiar to the resin in ion-exchangers, the adsorbtive capacity of the carbon is eventually depleted and the carbon either must be regenerated or replaced. Therefore a system incorporating activated carbon also requires careful monitoring to determine the effectiveness of the medium.
The present invention overcomes the undesirable characteristics, drawbacks and disadvantages of the prior art by providing a fluid treating method which employs metal particulate matter having a redox potential which relative to the redox potential of the undesirable constituents sought to be treated favors spontaneous oxidation-reduction reactions between the metal and the undesirable constituents. The metal particulate matter can be of varying mesh size, preferably of from 4 to 30 mesh based on U.S. Standard screen sizes, of any desired shape and is typically arranged in a loose bed confined within a treating tank by means which prevent the escape of the particulate matter but which, at the same time, permit fluid flow therethrough. Alternatively, techniques for adhering the particles into an aggregate porous body with the surface areas freely exposed can be utilized. Suitable techniques for forming such aggregate porous bodies include sintering and processes wherein a binder is utilized which results in all, or substantially all, of the surface area of the particles freely exposed for contacting fluids to be treated therewith. An important embodiment of the present invention is directed to a water treating method which employs metal particulate matter such as for example aluminum, iron, steel, zinc, and copper, as well as mixtures and alloys thereof, to provide removal of undesirable contaminants such as chlorine and nitrates. In this regard, an important aspect of the present invention involves a discovery that such a method will provide economical and long lasting removable of such undesirable contaminants and thereby greatly eliminate the weak link in most treatment systems i.e. maintaining and monitoring the system on a relatively frequent basis.
Another feature of the present invention involves a method of using such a bed of metal particulate matter in conjuntion with another type of fluid treating aparatus such as a reverse osmosis process or an ion-exchange process. In this regard, an important aspect of the present invention involves the removal of undesireable elements and compounds such as chlorine which may be detrimental to the operation and life of other treatment methods such as reverse osmosis and ion-exchange processes.
Another feature of the present invention involves adjusting the pH of the fluid and subsequently passing it through such a bed of metal particulate matter. In this regard, an important aspect of the present invention involves regulating the pH of the fluid prior to treatment to enhance the removal of contaminants having pH dependent oxidation-reduction activities.
Another feature of the present invention involves the conjoint use of dual containers having beds of such metal particulate matter arranged in series with a pH feeder interposed therebetween. Such a method of fluid treatment allows the user to take advantage of the pH of the source fluid at the inlet of the first container to treat the contaminants that are more responsive to treatment at the original source fluid pH and then to adjust the pH to treat contaminants which may be more effectively treated at another pH value to subsequently treat the fluid again in the second container.
It is therefore, an important object to the present invention to provide an improved fluid treating method.
Another object of the invention is to provide a fluid treating method which is economical to use, which has a relatively long life so as to avoid frequent maintenance and monitoring, and which eliminates the need to regenerate the treating medium and, accordingly, the need to dispose of concentrated contaminants inherent in other conventional treatment processes such as reverse osmosis and ion-exchange processes.
Another object of the invention is to provide a novel method of treating undesirable constituents such as chlorine and nitrates present in a fluid such as water without concentrating such constitutents in the treating medium.
Another object of the invention is to provide a fluid treating method which includes treating the fluid by passing the raw fluid containing undesirable constitutents through a bed of metallic particulate matter characterized by a redox potential which relative to the redox potential of the undesirable constituents sought to be treated establishes conditions for spontaneous oxidation and reduction reactions between the metal particulate matter and the undesirable constituents when the fluid is in contact with the metal particles.
Another object of the present invention is to provide an improved method of treating fluids wherein the fluids are first passed through a bed of metallic particulate matter to treat undesirable constituents present such as chlorine which may be harmful to a conventional fluid treatment process such as a reverse osmosis process or an ion-exchange process and to then pass the fluid through such a conventional treatment process.
These objects and other objects and advantages of the invention are accomplished by providing a method for treating fluid which includes passing fluid containing undesirable elements and compounds through a bed of metal particulate matter. The particulate matter is preferably chosen from metals such as aluminum, zinc, iron, steel, and copper as well as mixtures and alloys thereof, having favorable redox potentials relative to the undesirable constituents such as chlorine and nitrates sought to be treated so as to establish conditions for spontaneous oxidation and reduction reactions between the metal particulate matter and the undersirable constituents when the fluid is in contact with the metal particles.
Although an important aspect of the present invention is directed to the treatment of water especially drinking water, it will be appreciated that the method of this invention may also find advantageous utility in the treatment of a variety of other source fluids with various different undesirable contaminants. For purposes of illustration only therefore, this invention will, in most part, be described by reference to an embodiment wherein water is the source fluid being treated.
It has now been discovered that the composition of a given water supply can be altered with respect to certain contaminants therein such as dissolved chlorine and nitrates by bringing the water in contact with metals such as aluminum, iron, steel, zinc, and copper as well as mixtures and alloys thereof. For example, it has been noted that when water containing high concentrations of dissolved chlorine is passed through a canister housing metallic particulate matter such as brass that the detectable chlorine level of the effluent water is greatly reduced, if not totally eliminated.
It has further been discovered that such a method of fluid treatment is also effective under certain operating conditions to significantly reduce and/or eliminate the nitrate concentration of the effluent water. As a result of such findings, it is presumed that the present development may have widespread application to other types of inorganic contaminants such as hydrogen sulphide and sulphur dioxide to name but a few as well as organic contaminants.
Moreover, it is believed that the useful life of such a method of fluid treatment under normal operating conditions, would far exceed the useful life of other conventional treating systems. Accordingly, such a finding represents a considerable step forward in the art in that it helps to eliminate one of the major drawbacks of conventional systems, i.e. the need to frequently replenish the active source of treatment and the concomitant need to constantly maintain and monitor the system.
In addition such a method has wide spread potential application for a variety of domestic, commercial and industrial uses. For example noting that chlorine and iodine are effective anti-bacterial agents, drinking water, especially in a foreign locale, could be treated by initially chlorinating or iodizing the water and then the treated water could be transformed to a more palatable and safe form by passing the chlorinated or iodized water through a portable canister containing metal particles in accordance with the present invention.
As previously noted, this development is intended to have application to other fluid media besides water treatment including other liquid fluid media as well as gaseous fluid media by itself as well as gaseous fluid media dissolved in liquids. For example, removal of hazardous gasses especially the halogens such as chlorine, bromine, and flourine by passing those gasses through a canister housing a bed of metallic matter is contemplated by, and within the scope of, the present invention. Such an application may provide an alternate method of purifying contaminated air such as in a gas mask or may further be used as an alternative to or in conjunction with conventional scrubbing processes.
The method of the present invention contemplates the use of several different metals as well as mixtures and alloys thereof. It is hypothesized, without being limited to any particular theory of the invention, that the treatment process of the present invention is accomplished by spontaneous oxidation-reduction reactions. Accordingly it is believed that the metal particulate matter should be selected from a group of metals including mixtures and alloys thereof, which are relatively good redox agents relative to the undesirable constituents sought to be treated so as to establish conditions for spontaneous oxidation and reduction reactions between the metal particulate matter and the undesirable constituents when the fluid is in contact with the metal particulate matter.
The relative tendencies of different species to be reduced or oxidized can be predicted from their standard reduction potentials (E.degree. values at 25.degree. C.). By comparing the E.degree. values for different species it is possible to determine whether an oxidation-reduction will spontaneously occur. In accordance with the present invention, metals which are relatively good redox agents relative to the elements or compounds sought to be treated are those metals which are predicted to react spontaneously with such elements and compounds.
For example, chlorine dissolved in water having a pH of approximately 7 and at 25.degree. C. exists as HOCl and ClO.sup.- with HOCl predominating on the acid side and ClO.sup.- predominating on the base side. Assuming for simplicity that ClO.sup.- is the reacting species the following redox reactions are representative of those contemplated by the present invention:
______________________________________ Zn(s) .fwdarw. Zn.sup.2+ (aq) + 2e.sup.- E.sup.o = 0.76 V ClO.sup.- (aq) + H.sub.2 O + 2e.sup.- .fwdarw. Cl.sup.- (aq) + 2OH.sup.- (aq) E.sup.o = 0.89 V Zn(s) + ClO.sup.- (aq) + H.sub.2 O .fwdarw. Zn.sup.2+ + E = 1.65 V Cl.sup.- (aq) + 2OH.sup.- (aq) Cu(s) .fwdarw. Cu.sup.2+ (aq) + 2e.sup.- E.sup.o = -0.34 V ClO.sup.- (aq) + H.sub.2 O + 2e.sup.- .fwdarw. Cl.sup.- (aq) + 2OH.sup.- (aq) E.sup.o = 0.89 V Cu(s) + ClO.sup.- (aq) + H.sub.2 O .fwdarw. Cu.sup.+2 (aq) E = +0.55 V Cl.sup.- + 2OH.sup.- ______________________________________
As calculated, both zinc and copper should each react spontaneously with hypochlorite (ClO.sup.-) with the zinc theoretically being more spontaneous since it has the more positive potential.
In practice it has been found that a zinc and copper alloy, such as brass is more effective in the removal of dissolved chlorine than is either pure zinc or pure copper or a heterogeneous mixture thereof. In addition to the noted effectiveness of brass, brass is also a preferred metal from the viewpoint of chemical safety. This is especially true in aqueous media since brass does not have the violent reactivity to aqueous fluids as do metals such as pure sodium, potasium, calcium or zinc.
Where brass is the chosen metal, it has been found that washing the brass such as with a hydrochloric acid solution and then rinsing the brass will cleanse the surface of the brass of contaminants, such as iron filings or other foreign matter, which might interfere with the activity of the brass. However, it has additionally been noted that the surface of the brass which is exposed to the atmosphere or to a source fluid such as water may develop a greenish rust which may be a carbonate and/or oxide complex. When the surface itself is physically scraped to remove the greenish rust, the removed rust also shows excellent purifiying tendencies.
Qualitive analysis of water to which chlorine was added and which was treated by being passed through a bed of brass showed that such treating consistently effected a decrease in the amount of chlorine in the water. Set forth below are Examples I and II which describe quantitative anaylsis conducted by independent laboratories of the composition of the brass used to treat the water and of the water treated, respectively, both before and after treatment. Analysis of the brass, as described in Example I below, indicated that passing water through the bed of brass did alter the composition of the brass as might be expected if oxidation-reduction processes were occurring. As shown in Example II below, the independent laboratory analysis of the influent and effluent water passed through the bed of brass did confirm the virtual elimination of the chlorine contained in the influent water.